Methods of successive elution of components of hydrocarbons

ABSTRACT

The inventive technology may involve, in particular embodiments, novel use of a non-porous, high surface energy stationary phase to adsorb, in reversible fashion, the most polar component of a resins fraction of an input hydrocarbon when a mobile phase is passed over the stationary phase. Such reversible adsorption prevents irreversibly adsorption of such components on active stationary phase(s) downflow of the non-porous, high surface energy stationary phase, thereby conserving stationary phase costs and increasing resolution of resins elutions, and accuracy of hydrocarbon component results. Aspects of the inventive technology may also involve a novel combination of a solubility based asphaltene component fractionating and analysis method and an adsorption chromatography method for separating and/or analyzing saturate, aromatics and resins components of an input hydrocarbon.

This US non-provisional patent application is a continuation of, andclaims priority to, U.S. application Ser. No. 13/237,568, filed Sep. 20,2011, said application incorporated herein in its entirety by reference.

GOVERNMENT LICENSE RIGHTS

This invention was made with government support under FHWA ContractDTFH61-07-D-00005 awarded by the U.S. Department of Transportation. Thegovernment has certain rights in the invention, including “march-in”rights, as provided for by the terms of U.S. Department ofTransportation under FHWA Contract DTFH61-07-D-00005.

BACKGROUND OF THE INVENTION

Knowing the chemical composition of hydrocarbons (including but notlimited to petroleum oils and asphaltic materials) is critical inapplications such as improving the performance of bituminous roadways aswell as improving refining and oil production efficiency. Certainembodiments of the inventive technology disclosed herein combineinnovative features that provide a comprehensive, automated separationof oils in a manner that has not yet been achieved. This separationprovides quantitative information about the relative amounts of severalfractions using automated, normal phase chromatography coupled with anovel solubility-based separation of asphaltenes, saturates, naphthenes,aromatics, two subfractions of polars, and three solubility subfractionsof asphaltenes. The generated data provide valuable insight intocompositional differences between different oils and asphalt binders,the internal chemical changes which occur due to aging or processing,and processing generally. The results can be used in establishingcompatibility and for predictive modeling, process control, andimproving processing efficiency and yield, inter alia.

Adsorption Chromatography Petroleum Separations:

Separating a material into its constituent parts is often necessary indefining its composition. Separations of oils using normal phasechromatography have been around for several decades. One early versionof such type of analysis was developed by Corbett who separated asphaltsinto saturate, naphthene aromatic, polar aromatic and asphaltenefractions. A similar procedure was described by Jewel et al., in whichcrude oil or asphalt was separated into saturate, aromatic, resin, andasphaltene (SARA) fractions.

Using well known procedures, before these separations can be performed,the oils are usually first separated into two solubility classes by agravimetric separation utilizing a low polarity hydrocarbon solvent suchas isooctane, pentane, or heptane. The soluble material is by definitioncalled the maltenes or petrolenes. The insoluble material is, bydefinition, called asphaltenes. The gravimetric asphaltenes/maltenesseparation typically takes 24 hours. The chromatographic separation ofmaltenes takes another day. Certain conventional techniques to separatethe maltenes employ gravimetric open-column normal-phase adsorptionchromatography using polar stationary phases such as activated silicagel or activated aluminum oxide. If the asphaltenes are to be furtherseparated gravimetrically into two solubility subfractions such ascyclohexane soluble and cyclohexane insoluble, it may take an additionalday.

Again, using conventional methods, the maltenes are often separated intothree fractions by normal-phase liquid chromatography: saturates,aromatics, and resins/polars. The saturates fractions consist of bothlinear, branched and naphthenic fully saturated organic molecules of lowpolarity containing carbon and hydrogen and essentially no hetero-atoms.A molecule in the aromatics fraction contains mainly carbon andhydrogen, possibly some thiophenic sulfur, few if any heteroatoms, andis distinct from the saturate fraction by containing one or morearomatic rings. The resins and asphaltenes fractions both contain manyaromatic rings including highly colored pericondensed aromaticstructures, with many polar substituents.

Rod Chromatography: Approaches for SARA separation can be divided intotwo main groups. The first method that has been widely utilized uses atechnique known as thin-layer chromatography (TLC), and when combinedwith flame ionization detection (FID) becomes semi-automated. This isknown as the Iatrocsan method in which capillary thin layerchromatography is conducted with whole oils on silica or alumina rods asa stationary phase, followed by evaporating the elution solvent and thenslowly passing the rods through the flame of a flame ionization detectorto provide information on the relative amounts of the fractional zoneson the rod. The Iatrocsansystem typically elutes the fractions in asequence of solvents consisting of a linear alkane, cyclohexane,toluene, and dichloromethane:methanol mixtures. However, the Iatrocsanmethod has severe drawbacks including variable response factors for thedifferent fractions, relatively high amounts of polar compounds retainednear the spot location on the TLC rod, and aromatics grouping togetherto act like resins during separation. The separation is not veryrepeatable and there is a chronic problem with the strongly adsorbed,asphaltene material which does not migrate up the rod.

Column Chromatography: The second type of method requires initialprecipitation of the asphaltenes by dissolving the sample in an excessof an alkane before further separation of the maltenes into thesaturate, aromatic, and resin (SAR) fractions by liquid chromatography.Typical methods for the asphaltene separations are described in ASTMD3279, ASTMD4124 or similar. Many variations of the SAR separation havebeen developed using amino, cyano, or alumina columns including severalautomated or semi-automated methods utilizing high performance liquidchromatography (HPLC). Radke et al. described a semi-automated, mediumpressure liquid chromatography system to separate maltenes involvingthree analytical columns and three pre-columns in which the pre-columnshad to be re-packed between each injection. Variations for automatedseparations of the maltenes are typically performed using silica gelderivatized with aminopropyl or cyano functional groups. These typicallydo not provide fully resolved separations of saturates and aromatics andirreversible adsorption occurs on the columns due to resins and solubleasphaltene-type component molecules. A published version of an HPLC SARAmethod in the laboratory that uses chemically bonded aminosilanestationary phase for an automated SAR separation of crude oil malteneshas been evaluated and, while the authors claim that it also works onbituminous material, no data were presented to support this assertionand attempts to desorb the most polar fractions of asphalt from theirsystem were unsuccessful, resulting in poor recovery and fouling of thecolumn. Fan and Buckley developed a method that used two aminosilanecolumns. However, HPLC SARA methods that use chemically bondedaminosilane stationary phase of crude oil maltenes result in fouling ofthe column because of irreversible adsorption of resins. While theirsystem appears to work well for crude oils, the most polar components ofthe resins fraction of asphalt became irreversibly bonded to the column.Further, the saturates and aromatics fractions are not completelyseparated in the Fan and Buckley system. It was evident that a newsystem was needed for asphalt and heavy oils that performs the SARseparation without fouling the column and that allows full recovery ofthe resins fraction.

This inventive technology, in embodiments, involves a novel combinationof two modes of separation/analysis for hydrocarbons such as, e.g.,bitumen and oils, including but not limited to petroleum oils, asphalt,coal liquids and shale oils. In embodiments able to quantify asphaltenicconstituents, one component of the combined separation is an automatedsolubility separation in which asphaltenes are precipitated within aground polytetrafluoroethylene (PTFE)-packed column. This may bereferred to as the AsphalteneDeterminator (AD) separation, and may be asdescribed in U.S. Pat. No. 7,875,464 (perhaps supplemented by disclosureherein). In the second component, the material which is not precipitatedmay be passed onto a series of adsorption chromatographic columns bynormal-phase adsorption liquid chromatography for separation intosaturates, aromatics, and resins/polars (SAR) components. The SAR(saturates, asphaltenes and resins) separation may utilize threeseparate adsorption chromatography columns packed with differentsorbents. The first column may be packed with high surface energy,non-porous material to reversibly adsorb the very polar and highlyaromatic resins materials to keep them from adsorbing irreversibly onthe second (and perhaps the third) column. This packing can include astationary phase such as glass beads, metal particles, ceramics, orother materials (perhaps generally, non-porous, high surface energymaterials). The second column may be packed with a weakly adsorbingstationary phase (e.g., an activity reduced stationary phase) such asdeactivated silica or amino or cyano functional groups bonded to asilica matrix. The third column may be a highly active, stationary phasesuch as activated silica or alumina (perhaps an activity enhancedstationary phase). Flow switching and solvent switching valves may beused to provide a separation sequence in which the highly activatedstationary phase is not “activity-reduced” (deactivated) during orbetween separations, allowing for repeated separations without requiringthe stationary phases to be changed or discarded between runs. In a stepseparate from the adsorption chromatography separation of the maltenes,and perhaps after such adsorption chromatography steps are complete, theprecipitated asphaltene material on the PTFE column may be re-dissolvedusing one or more asphaltene solvents (i.e. solvents able to dissolve atleast a portion of the precipitated asphaltenes) to provide a solubilitydistribution profile of the asphaltene material. The result is acombined automated SAR separation coupled with the automated AD(asphaltene determinator) separation to provide a comprehensivecharacterization of materials.

SUMMARY OF THE INVENTION

When separating materials such as those in asphalt or heavy oils, themost polar compounds become difficult to desorb from a column that alsoadsorbs the aromatics (or a column that also adsorbs less polar resinscompounds). Particular embodiments of the inventive technology disclosedherein include a novel means of removing these materials from solutionbefore the first mobile phase (e.g., heptane solution, with injectedhydrocarbon dissolved therein) contacts the porous silica or aluminumoxide based sorbents (or more generally, the active stationary phases)used to adsorb less polar materials. When there is no interest incharacterizing the asphaltene component of a hydrocarbon and theasphaltenes are removed therefrom, after asphaltenes are precipitatedfrom oil and filtered using heptane, the resulting heptane solution ofmaltenes has a brown color due to the presence of pericondensed aromaticcompounds that did not precipitate with asphaltenes. After a shortperiod of time, a brown varnish type of coating appears on the surfaceof the inside walls of the glass container with the heptane maltenessolution (See FIG. 1). Chemically, this varnish material has been foundto be similar to the pericondensed aromatic material found inasphaltenes. However, this material remains in the heptane solutionduring the filtration steps. It is easily desorbed from the glass withtoluene or methylene chloride.

This observation has led us to initiate the first use of a column packedwith glass beads (generally, a non-porous, high surface energystationary phase) to precede silica or aluminum oxide columns in a SARseparation to remove the highly pericondensed material so it does notreach the latter, downflow stationary phases. Thus, one primary noveltyof this invention is the use of non-porous high surface energy materialto reversibly adsorb the most polar resins (and or the most aromaticpolar fractions) from maltenes using a liquid chromatography system. Theless polar materials can then pass through one or more subsequentcolumns packed with amino, cyano, silica or alumina stationary phases toseparate the saturates, aromatics and remaining resin fractions. Thisinvention is intended to include separation of any hydrocarbon includingpetroleum material such as residua, bitumen, crude oil, processedmaterials or products, asphalt, or non-petroleum materials such asadditives or rejuvenators, and oil using a column packed with glassbeads or other non-porous, high surface energy, typically non-polarsurface packing such as metals or ceramics to reversibly adsorb the mosthighly active pericondensed aromatic resins material prior to anysubsequent columns or separation schemes.

Aspects of the inventive technology may also involve a novel combinationof a solubility based asphaltene component fractionating and analysismethod and an adsorption chromatography method for fractionating andanalyzing saturate, aromatics and resins components of an inputhydrocarbon.

One advantage of at least one embodiment of the inventive technology isincreased accuracy in results relative to amounts of constituents of aninput hydrocarbon.

One advantage of at least one embodiment of the inventive technology isan increase in distillate yield of a hydrocarbon that is analyzed (or,more particularly, a sample thereof that is analyzed). Such increase maystem from an enhanced or increased accuracy of results.

One advantage of at least one embodiment of the inventive technologystems from an ability to reuse a stationary phase over a plurality of“runs” through the separator apparatus (each run perhapsseparating/analyzing a different hydrocarbon sample) withoutcompromising accuracy of results of second or following “run(s)”. Ofcourse, such a capability may result in significant cost savings, asexplained further herein.

One advantage of at least one embodiment of the inventive technology isan increase in speed of analysis. Indeed, using certain embodiments ofthe inventive technology disclosed herein, time from input of ahydrocarbon sample to be analyzed to elution, analysis, and/orgeneration of results may be less than that found in conventionalmethods.

One advantage of at least one embodiment of the inventive technology isa reduction in polluting emissions (given a certain distillate yield ora certain hydrocarbon input to be processed).

Other advantages of the inventive technology, in embodiments, may be asdisclosed elsewhere in this specification, including the figures.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows Maltenes Varnish Adsorbed to Glass from Decanted HeptaneSolution of Vacuum Residuum Maltenes.

FIG. 2 shows a Flow Diagram for the Automated SAR Separation ofMaltenes.

FIG. 3 shows a Separation Profile for the Automated SAR Separation ofMaltenes.

FIG. 4 shows a Flow Diagram for the Automated SAR Coupled with theAsphalteneDeterminator.

FIG. 5 shows a Separation Profile for the Automated SAR Coupled with theAsphalteneDeterminator for the Separation of a Whole Residuum.

FIG. 6 shows Table 1. ELSD Area Percents from the Automated SARSeparation of Maltenes.

FIG. 7 shows Table 2. ELSD Area Percents from the Automated SAR Coupledwith the AsphalteneDeterminator Separation of a Whole Residuum.

FIG. 8 shows Table 3. Comparison of Automated and Gravimetric SARAResults for Lloydminster Vacuum Residuum.

FIG. 9 shows an example of an embodiment of an apparatus particularlysuited for SAR resolution. The primed numbers correlate with steps ofFIG. 2.

FIG. 10 shows an example of an embodiment of an apparatus particularlysuited for SARA resolution. The primed numbers correlate with steps ofFIG. 4.

DETAILED DESCRIPTION OF THE INVENTION

As mentioned earlier, the present invention includes a variety ofaspects, which may be combined in different ways. The followingdescriptions are provided to list elements and describe some of theembodiments of the present invention. These elements are listed withinitial embodiments, however it should be understood that they may becombined in any manner and in any number to create additionalembodiments. The variously described examples and preferred embodimentsshould not be construed to limit the present invention to only theexplicitly described systems, techniques, and applications. Further,this description should be understood to support and encompassdescriptions and claims of all the various embodiments, systems,techniques, methods, devices, and applications with any number of thedisclosed elements, with each element alone, and also with any and allvarious permutations and combinations of all elements in this or anysubsequent application.

A substance, such as a hydrocarbon 1 (whether it be any of a variety ofhydrocarbons, including but not limited to oils from fossil, biologicalor synthetic sources, or derived from biological/renewable oil sources(such as biomass), or oil shale, or even coal (perhaps using a FischerTropsch process), may be established or entrained into (and as part of)a first solvent mobile phase 3 via any well known manners (injection,for example). A hydrocarbon may be, as but a few examples, oil, crudeoil, a constituent of oil (e.g., maltenes 2), bitumen, binder, lightoil, heavy oil, dilbit, opportunity crudes such as heavy sour grades,oils and bitumen, extra heavy oil, high TAN crudes, whether diluted insolvent solution or not. A mobile phase is that which is flowed throughat least part of the apparatus, over one or more stationary phases. Assuch, the term mobile phase, before injection of a hydrocarbon, may be asolvent (e.g., heptane, in one example), but then, after injection, thesame mobile phase may be that solvent with a hydrocarbon (e.g., ahydrocarbon sample) dissolved therein, or perhaps with substancesdesorbed or precipitated therein.

The inert stationary phase 5 (in embodiments with a stationary phase),may be a substantially inert stationary phase, such that any reactivityis only, at the very most, de minimus (i.e., such that any reactivitydoes not unacceptably affect operational functionality). Typically, itmay be non-polar, and be very low friction. Adsorption to or within theinert stationary phase typically does not occur. An example ofsufficiently inert stationary phase media includepolytetrafluoroethylene (typically ground or rendered into particles(e.g., beads or smaller) in some manner). Saturates or other constituentcomponents of oil (such as aromatics, resins, and asphaltenes) may beeluted (whether because, as may be the case for saturates, they are notadsorbed onto any stationary phase, or because, as may be the case witharomatics, resins or asphaltenes, they are desorbed from a stationaryphase after being adsorbed onto that stationary phase (or, as is thecase with asphaltenes, dissolved after being precipitated within astationary phase). When a component of a hydrocarbon is eluted, it maycome out of the column, existing in solution with the mobile phase, andpass through the apparatus to, e.g., an analyzer. Components of ahydrocarbon (e.g., saturates, aromatics, resins and asphaltenes,including subfractions thereof) may be as defined herein, or may have acommon, well understood meaning to one of ordinary skill in the relevantart; additional information may be found in the Wiehe and Kennedyreference (cited in the information disclosure statement filed herewith,all of said references incorporated herein in their entirety), inaddition to other incorporated, cited references.

Active sorbents 6 (e.g., porous active sorbents such as the activealumina and active silica stationary phases) can be activity reduced (orsimply active, if the steps to reduce activity are not performed on thesorbent). Porous as used in this context may imply a porosity that is ator above the lowest porosity (volume of voids over total volume) thatstill allows for the adsorption intended; its precise value may changedepending on the stationary phase used and/or the mobile phase passedover the stationary phase. Typically, an active sorbent will have beenheated to remove surface water (e.g., heated to above 100 deg C. butbelow 500 deg C., or above 110 deg C. to 600 deg. C.). An activityreduced sorbent 7 (e.g., a weakly adsorbing stationary phase such as oneincluding activity reduced silica or alumina), perhaps referred toconventionally as a deactivated sorbent, while still a type of activesorbent, may only be sufficiently active to adsorb resins (that may passthrough the non-porous, high surface energy medium (e.g., glass beadstationary phase)), but sufficiently inactive so as to not adsorbaromatics, nor irreversibly adsorb the resins that it does adsorb.Non-porous in this context may imply a porosity that is at or below thehighest porosity that still prevents adsorption as intended; its precisevalue may change depending on the stationary phase used and/or themobile phase passed over the stationary phase. Activity of the activityreduced stationary phases may have been reduced by exposure of thesorbent (perhaps after the drying operation indicated above) to water oralcohol (perhaps in the form of the methylene chloride:methanol solventmobile phase). Certain activity reduced stationary phases may besufficiently inactive without such drying or deactivation procedures.Active stationary phases that have not undergone the deactivationprocess (such stationary phases may be conventionally referred to asactivated media, such as activated alumina or activated silica, whichmay have only undergone a heat-induced drying), may be, but are notnecessarily, referred to as activity enhanced stationary phases 8.Certain active stationary phases may even be a combination of activityenhanced and activity reduced stationary phases. Typically, the activestationary phase is porous, at least more porous than any non-porous,high surface energy stationary phase 8 such as glass beads, or metal orceramic particles. It is of note that the need for an activity reducedcolumn (e.g., a weakly adsorbing stationary phase) may be eliminated ifthe non-porous, high surface energy stationary phase has enoughnon-porous, high surface energy stationary phase (to eliminate the needfor the activity reduced column). Further, while silica and/or aluminamay be preferred active, porous stationary phases (whether activityreduced (conventionally referred to as deactivated), or activityenhanced (conventionally referred to as activated)), other normal phasechromatography sorbents may suffice, including but not limited to thosewith aluminum oxide, clay, bonded amino or cyano silica surfaces.

It is of note that the methods, and apparatus, described herein may beonly separation methods or apparatus (where the goal is not to analyze ahydrocarbon relative to its constituent fractions, but instead toseparate at least one constituent fraction thereof), or they may be onlyanalysis methods (where the goal is not separation of at least oneconstituent fraction from a hydrocarbon, but rather analysis of ahydrocarbon, such as analysis of percentage composition of one or moreof its constituent fractions), or they may be both (analysis andseparation). In the case of analysis methods, even where, because acertain constituent of the input hydrocarbon is non-existent (e.g.,there are no aromatics or resins), actual eluted amounts are zero, insuch a situation, it is still said that the particular constituent thatis intended to elute is in fact eluted (it's just that zero amount of itelutes). Diesel fuel, for example, may not have any resins (onlysaturates and aromatics).

As to the term “fluidic communication”, it is of note that “A” can be influidic communication (whether controllable or otherwise) with “B” evenif there's a non-conduit flow element (e.g., a stationary phasecontainer) between the two. This stems from the fact that flow can, ofcourse, pass through several flow elements (e.g., a stationary phasecontainer(s)), before reaching a downstream flow element. The termcontainer as used herein is a broad term, and includes but certainly isnot limited to columnar containers. Generally, fluidic communicationimplies an ability of a fluid, at least at certain times (where anycontrol devices that may impact that flow are adjusted to allow suchflow), to flow from one component to another (via, e.g., any conduitsuch as tubes or piping). Further, more particularly relative to controlof flow (i.e., where two or more components are in controllable fluidiccommunication), a valve change even several stationary phases upflowfrom a flow element can divert flow from that downflow flow element. Assuch, such “remote” flow components can be in controllable fluidiccommunication. Control of a fluid flow generally implies some sort ofdevice or apparatus (flow control valve 10, such as a flow switching orsolvent switching valve, as but two examples) that can allow for flowshut off, flow diversion, flow reduction, flow redirection, and/or flowincrease, e.g. A flow switching valve may be a single valve that aloneaccomplishes a flow switch (e.g., from one mobile phase source toanother, whether gradually or in step-wise fashion, and/or redirectsthat new flow to a different stationary phase container), or it may beone of two or more valves that together accomplish an intended flowswitch (e.g., as where one valve shuts off flow from a mobile phasesource and, either at that time or later, another valve opens flow froma different mobile phase source). Further, fluidic communicationincludes, but does not require, controllable fluidic communication, andfluidic communication does not require fluid flow at all times (becausecontrolled fluidic communication can prevent such fluidic communicationif, for example, a valve is switched to redirect flow). As to flowcontrol componentry that serves to isolate a flow component (e.g., astationary phase container such as columnar container), component A maybe isolated from components B and C as long as flow through components Bor C doesn't go through component A.

Additionally, as mentioned, switching from one mobile phase to anothermay be done either gradually or in step-wise (more abrupt) fashion. Flowcontrol componentry may be used to accomplish the intended transition.Of course, where a gradual change is desired, shutting off the earliermobile phase and opening up the later mobile phase may occur more slowlythan when a step-wise, abrupt change is desired. Steps involving flow ofmobile phase don't mandate any particular transition, but insteadinclude all possibilities given the indicated flow (e.g., from abrupttransition to very gradual transition, including gradients in betweenthe two).

Of course, an important part of one aspect of the inventive technologyis the use of a non-porous, high surface energy stationary phase that isupflow of an activity enhanced stationary phase 9. Such may keep themost polar, aromatic resins materials away from the activity enhancednormal phase sorbent 8. The most polar, aromatic resins materialsadsorbed onto the non-porous, high surface energy stationary phase areadsorbed reversibly (they can be desorbed easily from the non-porous,high surface energy stationary phase), whereas they would adsorbirreversibly on the activity enhanced porous stationary phase (i.e.,such that they could not be desorbed therefrom), but for the non-porous,high surface energy stationary phase.

In particular embodiments of the inventive technology, flow componentry(e.g., valves) that causes resins desorbing mobile phase bypass of ahighly activated stationary phase (see step 3 of FIGS. 2 and 4) may beused to prevent deactivation of that highly activated stationary phase.Such may allow for re-use of that stationary phase, or at least obviatea labor intensive, costly “re-activating” step for that stationary phasefor it to be used during another run of the apparatus on a differenthydrocarbon sample.

A main advantage of certain aspects of the inventive technology is thatthe apparatus/methods afford complete, and automated, resolution of thesaturates and aromatics fractions. Other embodiments, supplemented withasphaltene fractioning steps and components (see FIGS. 4 and 10),resolve one or more of the asphaltene fraction, or resolves the entireasphaltene fraction upon providing compositional information thereabout.Further, one or more of the column packings (i.e., stationary phasemedia) used in the inventive technology may be less expensive than thosetypically used by conventional composition analysis schemes (such asvery expensive aminopropyl bonded silica, a column of which costsapproximately $800-$1000). The silica usable in the inventive method,and the glass beads and PTFE, are much less expensive. Further,conventional schemes often offer only non-resolved, or incompletelyresolved, overlapping constituent peaks (e.g., saturates and aromaticspeaks may overlap).

In particular embodiments, when there is no interest in characterizingan asphaltene portion of a hydrocarbon (see, e.g., FIGS. 2 and 9),maltenes in solution 2 may be injected into the first solvent mobilephase (from a first solvent source such as a first solvent container ofa first solvent). The maltenes (the component of oil that is left afterall or substantially all asphaltenes are removed, as by theconventionally known gravimetric precipitation and filtration asphalteneremoval method) may thus be dissolved in a low polarity solvent(pentane, heptane, hexane, isooctane as but a few examples), perhaps asa result of the procedure that generates them, and then injected (insolution) into the first mobile phase 3 (which also may be a lowpolarity solvent such as pentane, heptane, hexane, isooctane as but afew examples). These two solvents may, but need not, be identical. Attimes, the oil of interest may have so little asphaltenes to start outwith that the maltene generation procedure may be skipped; it may thenpossibly be input in undiluted form (presuming it is not overlyviscous). For example, a light crude oil with relatively few asphaltenescould possibly be injected directly, without dilution by a strongsolvent. It is of note that the term maltenes 2 (or any other componentof oil) can be used in reference to pure maltenes (i.e., undilutedmaltenes, with no solvent added), or maltenes in solution (i.e., asdissolved in a solvent, such as low polarity solvent). It is further ofnote that any of the apparatus may, as should be understood, duringoperation thereof, further comprise a mobile phase (e.g., a solventmobile phase) running through the flow conduits of the apparatus; suchmobile phase, of course, may have dissolved therein a hydrocarbon; themobile phase may also have a desorbed hydrocarbon component (saturates,aromatics, resins desorbed from certain stationary phases) orasphaltenes dissolved therein.

Continuing, when there is no interest in characterizing an asphalteneportion of a hydrocarbon, the asphaltenes (when there are asphaltenes)may first be removed from the original hydrocarbon, leaving maltenes(also deemed a type of hydrocarbon). Again, this may be done using awell known procedure (e.g., gravimetric precipitation and filtration).Then, in particular embodiments, a portion of the heptane solublematerial (maltenes) in solution may then be injected into the firstmobile phase so that it is brought in contact with the non-porous, highsurface energy 9 column (e.g., glass bead stationary phase) andcolumns(s) with active stationary phase 6 (activity enhanced stationaryphase 8 and possibly also an activity reduced stationary phase 7).Typically, the only precipitation seen in this scheme is thepreliminary, a-columnar (without a column, or without a stationaryphase) gravimetric precipitation and filtration of the asphaltenes (tocreate the maltenes). Reversible chromatographic adsorption of thehighly aromatic and polar resins materials on the non-porous, highsurface energy column precludes the adsorption of these same materialson the active (typically porous, whether activity enhanced or activityreduced) stationary phase(s) of the column(s) that are downflow (suchadsorption would be a highly undesired reversible adsorption, requiringan expensive and time consuming replacement of such active (typicallyporous) stationary phases). Indeed, at least one aspect of the inventivetechnology involves successive use, for a different hydrocarbon sample,of a particular bulk quantity of one or more stationary phases (i.e.,the very same particles of activity reduced silica, as but one example).Successive solvent mobile phases of increasing solvent strength may beadded, with flow control valve(s) being used to bypass particularstationary phases (as particularly described elsewhere in thisspecification). Separately eluted components (after saturates) may bearomatics and resins.

The SAR separation of asphalt binders was finally enabled by theinnovative use of a column filled with glass beads placed before thenormal phase separation columns to remove the most pericondensedaromatic asphaltene-like molecules from the maltenes (which do notprecipitate with asphaltenes). These molecules can then later bedesorbed from the glass beads (or other non porous glass, ceramic, ormetal surfaces) using a solvent stronger than heptane. This is importantbecause it is these components which typically, irreversibly adsorb ontonormal phase sorbents that are based on silica gel with or withoutchemical modification, and aluminum oxide. This has been a hindrance tothe successful, long term operation of automated SAR separations since astationary phase with strongly adsorbed components must be discardedafter each use because of the components that cannot be desorbed with astrong solvent. Another problem stems from the fact that strong solventsusually deactivate silica or alumina stationary phases such that suchdeactivated stationary phases are no longer able to fully separatesaturates and aromatics. This requires that such stationary phases bediscarded and changed frequently. The use of flow components such asswitch(es) and/or valve(s) can, in certain embodiments, keep the thirdmobile phase 20 (e.g., CH₂Cl₂:MeOH) off of the activity enhancedstationary phase and prevent it from deactivating such stationary phase.

As mentioned, when there is an interest in using a fully automated,single hydrocarbon sample input procedure to characterize theasphaltenic component of a hydrocarbon, an input that has not hadasphaltenes removed therefrom would typically be injected into the firstmobile phase. In such case, a relatively strong solvent (e.g.,chlorobenzene) that can dissolve the whole sample 12 and keep theasphaltenes in solution may be used to dilute the hydrocarbon 1 ofinterest because the oil is too viscous to be injected directly inundiluted form). An example is injection of 20 uL of a 10% (w/v)solution that includes 2 mg of a residuum or asphalt binder (bitumen).Even where an undiluted hydrocarbon is diluted in a solvent, and thatsolution is then input into a mobile phase, it is still said that ahydrocarbon is input into that mobile phase. If the oil weresufficiently non-viscous (sufficiently liquid), then a direct injectionof 2 mg may suffice. After injection of the hydrocarbon (viacontrollable hydrocarbon input 65, where controllable merely implies anability to start and stop the input, or merely allow input of a limitedamount of hydrocarbon), the first mobile phase, which ideally may be anylow polarity solvent (including, of course, a nonpolar solvent) that canprecipitate some of the asphaltenes within the inert stationary phase,should suffice. Examples may include but are not limited to: hexane,heptane, isooctane and pentane. While a low polarity first mobile phase(for methods that characterize the asphaltenic fraction) may bepreferred, it may not be necessary, as the critical requirement for thissolvent is that it precipitates any portion of the sample (e.g., theasphaltenic portion). It is of note that the first mobile phase ispreferably an alkane solvent regardless of whether the input hydrocarbonis a maltene or whether it includes asphaltenes. However, when theprotocol involves asphaltene separation (for resolution thereof, asshown perhaps in FIGS. 4 and 10), the first mobile phase 3 shouldadditionally be able to precipitate asphaltenes within the inertstationary phase.

The SARA procedure (saturates, aromatics, resins and asphaltenes) mayinvolve a novel combination of two modes—an asphaltenic mode (which maybe non-chromatographic and instead, solubility based), and an adsorptionchromatography mode dedicated to the separation and/or analysis ofsaturates and possibly also aromatics and resins—for separation/analysisof oils including but not limited to petroleum oils, bitumen, asphalt,coal liquids and shale oils. In embodiments that resolve asphaltenicconstituents, an initial step may be an automated solubility separationin which asphaltenes are precipitated within a groundpolytetrafluoroethylene (PTFE)-packed column using a non-polar solvent,perhaps as disclosed in U.S. Pat. No. 7,875,464, or as disclosed herein(said patent incorporated herein in its entirety). In the secondcomponent, the material which is not precipitated in the first step maybe passed onto a series of adsorption chromatographic columns forseparation by normal-phase, adsorption, liquid chromatography intosaturates, aromatics, and resins/polar aromatics (SAR) or other similar(e.g., naphthenic polar) components. The SAR separation may utilizethree separate adsorption chromatography columns packed with differentsorbents. The first adsorption column may be packed with high surfaceenergy, non-porous material 9 to reversibly adsorb the very polar andhighly aromatic resins materials to keep them from adsorbingirreversibly on the second downflow column (and/or other downflowcolumn). The second adsorption column may be packed with a weaklyadsorbing stationary phase 7 (activity reduced silica or alumina, as buttwo examples) that adsorbs the resins that pass through the firstadsorption column. The third adsorption column may be packed with ahighly active stationary phase 8 such as activity enhanced stationaryphase 8 (e.g., activated silica or alumina, as but two examples), forseparation of the aromatic components from the saturated hydrocarboncomponents. Flow control componentry (e.g., flow control valves 10) suchas flow direction valves and/or solvent switching valves may be used toprovide a separation sequence in which a highly activated stationaryphase is not deactivated (or have its activity reduced) during orbetween separations, allowing for repeated separations without requiringthe stationary phases to be regenerated, changed, or discarded betweenruns.

Briefly, in certain applications, where there is an interest in using afully automated, single hydrocarbon sample input procedure tocharacterize the asphaltenic component of a hydrocarbon (amongcharacterizing other components), a hydrocarbon solution of whole oil 12(i.e., that includes asphaltenes) in a strong solvent may be injectedinto a first mobile phase (heptane is one type of such mobile phase;other examples are listed herein) from a first mobile phase source 60.Thereafter, the asphaltenes precipitate within the inert stationaryphase 5 (e.g., within the column with substantially inert stationaryphase such as PTFE therein). The term “precipitation within a stationaryphase”, stationary phase container, or column indicates precipitation inthe solvent mobile phase (e.g., in heptane) within the pores of the bedof the stationary phase (e.g., PTFE). Such precipitation isnon-chromatographic. Steps, and components that follow (other than thoserelated to the inert stationary phase or the asphaltenes themselves, orthe use of solvent mobile phases specifically to dissolve precipitatedasphaltenes), may be as seen in those embodiments that are not designedto also elute (and possibly also analyze) asphaltenes. The first mobilephase soluble material may continue on to the non-porous, high surfaceenergy stationary phase and the remaining stationary phases (e.g.,active stationary phases 6, whether activity reduced 7 or activityenhanced 8 or a combination of the two). Adsorption chromatograph occursin such containers (e.g., columns). Aliphatic hydrocarbon material(saturates) may pass through all columns and elute first. The activityenhanced column (e.g., activity enhanced, or activated, silica) preventsthe aromatics from eluting with the saturates (because the aromatics areadsorbed, reversibly, onto the activity enhanced column). Thenon-porous, high surface energy stationary phase 9 (e.g., glass bead)and any activity reduced stationary phase column 7 (e.g., activityreduced silica or activity reduced alumina, as but two examples), adsorbthe resins material (perhaps referred to elsewhere herein as polarsmaterial). The most aromatic and polar resins materials are reversiblyadsorbed onto the non-porous, high surface energy stationary phaseinstead of irreversibly adsorbed onto any of the active stationaryphases (whether activity reduced or activity enhanced) that are downflowof it. Flow control valve(s) 10 may then be used to isolate the firstcolumn (the inert material column, which may preferably include PTFE)and the non-porous, high surface energy column. A second solvent mobilephase 19 (e.g., toluene or similar, which is stronger than the firstsolvent mobile phase), from a second solvent source 61, may then bebackflushed through the active columns, but not the non-porous, highsurface energy column, nor the inert stationary phase column; thisbackflush elutes aromatics. It is of note that any backflush or backflowof a mobile phase over a stationary phase typically involves backflowthrough that container (e.g., column), as where the flow directionthrough the column (e.g., of the second and third mobile phase) isopposite the flow direction of the first mobile phase through thecolumn. While FIGS. 9 and 10 don't show such backflow (indeed, they showforward flow through the stationary phases), they do show a reversedorder of flow of the second and third mobile phases as compared with thefirst mobile phase (for example, the second mobile phase hits theactivity enhanced stationary phase before it hits the activity reducedstationary phase). During such reversed order of flow of the second orthird mobile phases, either forward or back flow through the individualstationary phases is possible in embodiments of the inventivetechnology. Then, using a flow control valve(s), a third solvent mobilephase 20 (methylene chloride:methanol, chloroform:methanol, methylenechloride:ethanol, trichloroethane:methanol, cyclohexanone:methanol, asbut a few examples), from a third solvent source 62, which is strongerthan the second (and first) solvent mobile phases, may then bebackflushed through the non-porous, high surface energy column and anyactivity reduced stationary phase that may be used, but not through theactivity enhanced stationary phase (because the alcohol, e.g., methanol,would deactivate it), nor through the inert stationary phase. Thiselutes the polars (resins) that were adsorbed onto the non-porous, highsurface energy column and any activity reduced stationary phase that maybe used (perhaps resulting in two resins peaks).

Such columns—the non-porous, high surface energy stationary phasecolumn, the activity enhanced stationary phase column, and any activityreduced stationary phase column that may be used—are then isolated usingflow control valve(s), and the asphaltenes (or a portion thereof) of theinert stationary phase column (e.g., PTFE column) that were earlierprecipitated within the inert column are dissolved using at least oneasphaltene solvent. It is of particular note that the term asphaltenesolvent is a solvent that can dissolve one or more asphalteniccomponents (i.e., at least a portion of asphaltenes) of a hydrocarbon.In order to gain more information on the compositions of differentasphaltenes, solvents of increasing strength may be used. For example, afirst asphaltene solvent mobile phase, from a first asphaltene solventmobile phase source 22 (for the asphaltene dissolution stage) may becyclohexane, with a second asphaltene solvent mobile phase from a secondasphaltene solvent mobile phase source 23 being toluene, and a third(from third asphaltene solvent mobile phase source 24) being methylenechloride:methanol, with each dissolving a different asphaltenesubfraction, resulting in the passage of this subfraction(s) to analysiscomponentry, if desired. The asphaltene dissolution protocol may be asdisclosed in U.S. Pat. No. 7,875,464. Alternate mobile phases includebut are not limited to benzene, xylenes, mixtures of cyclohexane andheptane, mixtures of toluene and heptane, chloroform, cyclohexanone. Theresult, in particular embodiments, is a fast, accurate method to fullycharacterize the composition of oils.

It is also of note that at times, only information regarding oneconstituent fraction of the oil, such as the saturates fraction, may beof interest. In such case, perhaps additional steps and components(e.g., additional mobile phases) that are non-essential to gleaning thedesired information may be eliminated from the procedure. Further,regardless of whether the inventive method involves analysis (e.g.,compositional determination) of asphaltenes, the need for a weaklyadsorbing stationary phase (activity reduced stationary phase) may beobviated if a sufficiently large amount of the non-porous, high surfaceenergy stationary phase is used. If such sufficiently large amount ofthe non-porous, high surface energy stationary phase is used, in certainapplications, the activity reduced stationary phase may possibly beeliminated, resulting in a process that still provides acceptableresolution for the intended application. It is of note that FIGS. 2 and4 show steps in at least a few embodiments of the inventive technology.As mentioned, depending on the goals of the separation/analysis, certainsteps (e.g., the aromatics and resins elution steps (steps 2 and 3 ofFIGS. 2 and 4), and the asphaltene elution steps (steps 4-6 of FIG. 4))may be selectively, perhaps individually, eliminated. Further, dependingon the goal(s) of the procedure, certain components may not be required.For example, if there is no interest in resolving an asphaltenecomponent, then the inert stationary phase may not be necessary. If oneis interested only in the highly alkyl substituted pericondensedaromatics fraction of the asphaltenes, then the other alsphaltenesolvents may be eliminated. Also, as mentioned, in applications wherethere is interest in resolving an asphaltene component, if enough of theinert stationary phase is used, the activity reduced stationary phasemay be eliminated. It is also of note that the diagrammaticrepresentations of the SAR and SARA separation and analysis apparatus asshown in FIGS. 9 and 10, respectively, each show only one possible wayof using flow control valves so as to achieve the flow of the mobilephases as intended (e.g., to their intended stationary phases). Uponpresentation of this disclosure, other arrangements could be designed byone of ordinary skill in the relevant art.

As should be understood, aspects of the inventive technology may involvehigh surface energy materials (e.g., the non-porous, high surface energymedia, such as glass beads, of one of the stationary phase columns).Such high surface energy material will have a surface energy (perhapsotherwise known as surface free energy or surface tension) of greaterthan or equal to 100 mN/m; other types of such material may perhaps haveonly greater than or equal to 40 mN/m. Generally, high surface energymaterial implies a surface energy greater than or equal to 40 mN/m. Ontothis high surface energy material is adsorbed components of the oil(such as very aromatic material, inter alia) that themselves typicallyhave surface energies that are from about 40-100 mN/m. As to the weaklyadsorbing stationary phase (when used), such as activity reduced silicaor activity reduced alumina (as but two examples)—in one example it isany stationary phase (such as a porous sorbent) that is activity reducedvia exposure of the sorbent (perhaps after a surface drying via heatingoperation indicated elsewhere in this description) to water or alcohol(perhaps in the form of the methylene chloride:methanol solvent mobilephase). It is also of note that where the viscosity of an input oil isgreater than, e.g., 20 cP, there may be a need to dilute such oil with asolvent before injecting it into the first mobile phase.

Often, the purpose of any of the inventive methods disclosed herein isanalysis of the input hydrocarbon; typically, that analysis means acharacterization in some manner (typically numerically) of one or moreof the various constituents of the input hydrocarbon (e.g., saturates,aromatics, resins, naphthenes, asphaltenes, subfractions of polars, andsolubility subfractions of asphaltenes, as but a few examples). Often,that characterization relates to the amount of the constituent(s) ofinterest in the hydrocarbon, whether on a percentage or other basis,where that constituent(s) of interest is eluted from the apparatus.Analysis componentry 25 may include, but is not limited to well knowndetectors, such as ELSD (evaporative light scattering detector), opticalabsorbance (which include UV and visible), refractive index, CAD(charged aerosol detector), and other spectrometers. Information gleanedfrom analysis can additionally, or instead, aid in assessingcompatability of the oil or hydrocarbon material associated with theinput hydrocarbon (e.g., maltenes, or perhaps one containingasphaltenes) conducting predictive modeling, selecting feed (unprocessedhydrocarbon input) for process optimization, and effecting processcontrol. It is also of note that current methods, whether because ofunresolved peaks of eluted materials or for other reasons, do not affordthe accuracy afforded by the instant inventive technology. Further, highcosts associated with non-reusable stationary phases may force somerefineries at times to forego any SAR or SARA determination whatsoever.Regardless, refineries (a term that includes but certainly is notlimited to laboratories that analyze hydrocarbons) using conventionaltechnologies are processing hydrocarbons with limited information aboutthem (e.g., about coking onset) and their compositional makeup. As such,in order to avoid coke formation, or form only a small amount of cokeduring processing (or in order to avoid fouling of catalysts and/or heatexchanges, or only cause minimal fouling, or in order to avoid orminimize formation of emulsions in desalters, all during or as a resultof processing), relatively conservative processing conditions are used.Indeed, the lack of information about the unprocessed (or partiallyprocessed) input hydrocarbon causes process operators to not produce asmuch end product(s) (e.g., gasoline, fuel oil, lubricating oils, dieselfuel, kerosene, jet fuel, tar, heavy fuel oil and asphalt) as couldpossibly be produced if they had more accurate, reliable informationregarding compositional makeup, and could “push”, or further adjustprocessing conditions (residence time, pressure, temperature, catalystuse, etc.), to produce more product while still avoiding coke formation(or only forming an small amount of coke) or experiencing otherundesired outcome (e.g., any or too much fouling, unacceptable amountsof emulsion generation in desalters). The more accurate the information,the more efficient the process is because, e.g., coke onset estimationbecomes more accurate as a result. As such, particular embodiments ofthe inventive technology disclosed herein enable greater end productproduction—a supplemental end product, or an end product not producedusing conventional technology for a given hydrocarbon processor input(refinery input). In this way, carbon dioxide and other undesiredemissions (such as SOx, NOx, as but a few examples, all generally termedpollutants) can be reduced for a given production of a hydrocarbon endproduct (or a supplemental amount of oil can be produced for a certainamount of emissions, or for a given hydrocarbon processing expenditure,or for a given emissions allotment, allowance or expenditure). Suchefficiency has obvious cost savings implications and, if a cap and tradescheme is ever legislated, will result in emissions credits associatedwith this “reduced emissions per produced end product” that, having amonetary value (estimated in 2011 to be from $20/ton to $140/ton, whichmay indeed change depending on the market conditions), can be traded onthe market. Indeed, the owner of the inventive technology claims thatmarket value, in addition to the supplemental oil per hydrocarbon input,or per emissions output afforded upon use of the inventive technology,inter alia.

As an example of calculations that suggest the magnitude of costssavings attributable to the inventive technology based on an estimate of2.3 million barrels of heavy ends per day of thermal cracking and cokerfeed that can be produced from distillation operations in the U.S., anindustry-wide 1% increase in distillate yield (end product) from safelycutting deeper into a heavy oil during distillation (perhaps a low end,conservative estimate) would result in about 23,000 bpd of supplementalend product, worth approximately $230,000/day, assuming a differentialprice between residua and distillate of $10/bbl. Further, there would besignificant energy savings involved using aspects of the inventivetechnology, as coking operations use about 166,000-258,000 Btu perbarrel of feed (USDOE 1998). For each 1% decrease in thermal crackingand coker feed (near 23,000 barrels per day in 2011, (USEIA 2011)),there would be a potential energy savings of about 3.8-5.9 billion Btufor residua that do not need to be heated for coking, since they willhave been recovered in an optimized distillate stream. This alsocorresponds to a lowering of carbon dioxide from fuel that is not burnedin coking operations. Residual fuel used as the heat source producesabout 174 pounds of carbon dioxide per million Btu generated. Thus, inthe U.S., the reduction in carbon dioxide emissions for each 1%industry-wide distillation efficiency improvement may be about 331-515tons per day (2011 figures). Given the above-mentioned monetary per tonemissions estimate ($20-$140/ton), at 515 tons/day (188,000 tons/yr),which certainly could increase, market value for avoided CO₂ emissions(valued according to market value of traded emission credits) could be$3,760,000/yr up to $26,320,000/yr for each 1% gain in efficiency. So, a5% efficiency gain would yield $18,800,000 to $131,600,000/yr in CO₂emission value. Of course, actual savings/costs/value could be greater(including the 1% gain); these are merely estimates.

Laboratory Results:

The following laboratory conditions and results, while presented usingparticular data, are not intended to limit the scope of the inventivetechnology.

Automated SAR Separation:

The flow diagram for an example SAR separation that has beensuccessfully demonstrated with repeat injections is illustrated in FIG.2. For the normal phase chromatography method, 190 μL portions of 1%(wt/vol) heptane maltenes dissolved in heptane are injected into thesystem. Solvent flow rates are 2 mL/min. Following Step 1 in FIG. 2, thesaturates elute with heptane through a glass bead column, deactivated(activity reduced) silica column, and activated (activity enhanced)silica column. The highest surface energy resins adsorb on the glassbeads, and other resins adsorb to the deactivated silica column. Thearomatics may adsorb on the deactivated silica column and partially onthe activated silica column. Step 2 may be a back flush with toluenethrough the deactivated silica and activated silica columns to elute thearomatics. The final step may involve back flushing the deactivatedsilica and glass bead columns with CH₂Cl₂:MeOH (98:2 v:v) to elute theresins molecules. The entire system is then regenerated with an initialtoluene back flush followed by heptane. Because the activated silicacolumn is never contacted with methanol, it does not become deactivatedand thus it is suitable for many repeat separations without requiringstationary phase reactivation or repacking.

The silica used for the example is grade 62, 60-200 mesh, 150 Å fromSigma Aldrich activated at 120° C. overnight. Glass beads are 150-212 μmunwashed from Sigma. The separation is conducted at 30° C. with a columnheater and it utilizes automated 4-port and 6-port switching valves todirect the flows as illustrated in FIG. 2.

The solvent switching sequence used is provided below. Column 1 ispacked with glass beads, column 2 is packed with silica gel that becomesdeactivated (activity reduced) by contact with the methylenechloride:methanol (98:2 v:v) solvent and is designated the deactivated(DA) (activity reduced) silica gel column, and column 3 is the activated(A) (activity enhanced) silica gel column.

-   -   1. 0-25 minutes, heptane through columns 1, 2, and 3.    -   2. 25-48 minutes, toluene back flush through columns 3 and 2.    -   3. 48-70 minutes, methylene chloride:methanol (98:2 v:v) back        flush through columns 2 and 1.    -   4. 70 begin toluene followed by heptane flushing to prepare for        next injection.

A separation profile of 2 mg residuum in heptane maltenes is provided inFIG. 3. An evaporative light scattering detector (ELSD), a type ofanalysis equipment, is used for quantifying fractions while opticalabsorbance detection at 260 nm provides evidence that aromatics are noteluting with the saturates fraction, and 500 nm absorbance detects theelution of pericondensed aromatic molecules in the aromatics and resinsfractions. The ELSD area percent corresponds to weight percent ofmaterial. In this separation, there are two resins subfractions, theglass bead resins which elute first, followed by deactivated silicaresins. The saturates fraction which elutes with heptane consists of asingle large peak followed by a broader shoulder peak. This latter peakprobably is due to naphthenes and could contain small amounts of highlyalkyl substituted structures. It could also olefins, or very highlyaliphatic substituted aromatic components. The toluene back flush elutesthe aromatics. Resins/polars are eluted with methylene chloride:methanol(98:2 v:v). Alternative solvents or similar combinations of sorbentscould be used in variances of this separation.

The repeatability of the separation from a series of injections of 2 mgheptane maltenes is provided in Table 1 (See FIG. 6). The consistentarea percent for the saturates fraction is an indicator that theactivated silica column is not becoming deactivated.

Automated SAR/AD Combined Separation:

A main feature of this invention is coupling the automated SAR with theautomated AsphalteneDeterminator separation which is used to separatethe asphaltenes into three solubility fractions consisting of highlyalkyl substituted pericondensed aromatics, alkyl substitutedpericondensed aromatics, and pre-coke/polar aromatics (14-17). The flowschematic for the combined SAR separation coupled with theAsphalteneDeterminator separation is provided in FIG. 4. The solventswitching sequence is provided below. The last three columns are thesame as those used in the SAR separation described previously. A columnpacked with 40-60 mesh polytetrafluoroethylene (PTFE) is place beforethese columns for the initial on-column precipitation of asphaltenes onan inert stationary phase. Column 1 is packed with ground PTFE, column 2is packed with glass beads, column 3 is packed with silica gel thatbecomes deactivated by contact with the methylene chloride:methanol(98:2 v:v) solvent and is designated the deactivated (DA) (activityreduced) silica gel column, and column 4 is the activated (A) (activityenhanced) silica gel column.

-   -   1. 0-28 minutes, heptane forward flow through columns 1, 2, 3,        and 4.    -   2. 28-48 minutes, toluene back flush (or backflow) through        columns 4 and 3.    -   3. 48-68 minutes, methylene chloride:methanol (98:2 v:v) back        flush through columns 3 and 2.    -   4. 68-78 minutes, toluene back flush followed by heptane back        flush through columns 4, 3, and 2.    -   5. 78-88 minutes, cyclohexane forward flow through column 1    -   6. 88-98 minutes, toluene forward flow through column 1    -   7. 98-108 minutes, methylene chloride:methanol (98:2 v:v)        forward flow through column 1    -   8. 108, minutes, begin toluene followed by heptane back and        forward flow/flush to prepare for next injection

The separation profile for 20 uL of a 10% (wt·vol) solution (2 mg) ofLloydminster vacuum residuum in chlorobenzene with the coupled SAR/ADsystem is illustrated in FIG. 5. By automating the entire process in acomprehensive scheme using only a 2 mg whole sample without priorremoval of asphaltenes, the entire separation can be performed in lessthan two hours.

Repeat injection data for 2 mg portions of Lloydminster vacuum residuumin chlorobenzene are provided in Table 2 (See FIG. 7). The dataillustrate that the results are consistent for a series of repeatinjections. The repeatability of the relative saturates peak areapercent indicates that the activated silica gel packed column remainsactivated.

Gravimetric separations data for Lloydminster vacuum residuum werecompared with the automated method data. The data from the automatedseparation compared favorably with data generated using a gravimetric,open column procedure using 35 g of the same activated silica gel usedin the activated silica column for the automated separation (grade 62,60-200 mesh, 150 Å from Sigma Aldrich activated at 120° C. overnight) toseparate 0.35 g maltenes using 400 mm long×19 mm ID glass column,following gravimetric precipitation of heptane asphaltenes (Table 3—seeFIG. 8).

Additional Information: As can be easily understood from the foregoing,the basic concepts of the present invention may be embodied in a varietyof ways. It involves both hydrocarbon constituent separation and/oranalysis techniques as well as devices to accomplish the appropriateseparation and/or analysis. In this application, the separation and/oranalysis techniques are disclosed as part of the results shown to beachieved by the various devices described and as steps which areinherent to utilization. They are simply the natural result of utilizingthe devices as intended and described. In addition, while some devicesare disclosed, it should be understood that these not only accomplishcertain methods but also can be varied in a number of ways. Importantly,as to all of the foregoing, all of these facets should be understood tobe encompassed by this disclosure.

The discussion included in this application is intended to serve as abasic description. The reader should be aware that the specificdiscussion may not explicitly describe all embodiments possible; manyalternatives are implicit. It also may not fully explain the genericnature of the invention and may not explicitly show how each feature orelement can actually be representative of a broader function or of agreat variety of alternative or equivalent elements. Again, these areimplicitly included in this disclosure. Where the invention is describedin device-oriented terminology, each element of the device implicitlyperforms a function. Apparatus claims may not only be included for thedevice described, but also method or process claims may be included toaddress the functions the invention and each element performs. Neitherthe description nor the terminology is intended to limit the scope ofthe claims that will be included in any subsequent patent application.

It should also be understood that a variety of changes may be madewithout departing from the essence of the invention. Such changes arealso implicitly included in the description. They still fall within thescope of this invention. A broad disclosure encompassing both theexplicit embodiment(s) shown, the great variety of implicit alternativeembodiments, and the broad methods or processes and the like areencompassed by this disclosure and may be relied upon when drafting theclaims for any subsequent patent application. It should be understoodthat such language changes and broader or more detailed claiming may beaccomplished at a later date (such as by any required deadline) or inthe event the applicant subsequently seeks a patent filing based on thisfiling. With this understanding, the reader should be aware that thisdisclosure is to be understood to support any subsequently filed patentapplication that may seek examination of as broad a base of claims asdeemed within the applicant's right and may be designed to yield apatent covering numerous aspects of the invention both independently andas an overall system.

Further, each of the various elements of the invention and claims mayalso be achieved in a variety of manners. Additionally, when used orimplied, an element is to be understood as encompassing individual aswell as plural structures that may or may not be physically connected.This disclosure should be understood to encompass each such variation,be it a variation of an embodiment of any apparatus embodiment, a methodor process embodiment, or even merely a variation of any element ofthese. Particularly, it should be understood that as the disclosurerelates to elements of the invention, the words for each element may beexpressed by equivalent apparatus terms or method terms—even if only thefunction or result is the same. Such equivalent, broader, or even moregeneric terms should be considered to be encompassed in the descriptionof each element or action. Such terms can be substituted where desiredto make explicit the implicitly broad coverage to which this inventionis entitled. As but one example, it should be understood that allactions may be expressed as a means for taking that action or as anelement which causes that action. Similarly, each physical elementdisclosed should be understood to encompass a disclosure of the actionwhich that physical element facilitates. Regarding this last aspect, asbut one example, the disclosure of a “analyzer” should be understood toencompass disclosure of the act of “analyzing”—whether explicitlydiscussed or not—and, conversely, were there effectively disclosure ofthe act of “analyzing”, such a disclosure should be understood toencompass disclosure of an “analyzer” and even a “means for analyzing”Such changes and alternative terms are to be understood to be explicitlyincluded in the description. Further, each such means (whetherexplicitly so described or not) should be understood as encompassing allelements that can perform the given function, and all descriptions ofelements that perform a described function should be understood as anon-limiting example of means for performing that function.

Any patents, publications, or other references mentioned in thisapplication for patent are hereby incorporated by reference. Anypriority case(s) claimed by this application is hereby appended andhereby incorporated by reference. In addition, as to each term used itshould be understood that unless its utilization in this application isinconsistent with a broadly supporting interpretation, common dictionarydefinitions should be understood as incorporated for each term and alldefinitions, alternative terms, and synonyms such as contained in theRandom House Webster's Unabridged Dictionary, second edition are herebyincorporated by reference. Finally, all references listed in the list ofReferences To Be Incorporated By Reference In Accordance With The PatentApplication or other information statement filed with the applicationare hereby appended and hereby incorporated by reference, however, as toeach of the above, to the extent that such information or statementsincorporated by reference might be considered inconsistent with thepatenting of this/these invention(s) such statements are expressly notto be considered as made by the applicant(s).

Thus, the applicant(s) should be understood to have support to claim andmake a statement of invention to at least: i) each of the separationand/or analysis devices/apparatus as herein disclosed and described, ii)the related methods disclosed and described, iii) similar, equivalent,and even implicit variations of each of these devices and methods, iv)those alternative designs which accomplish each of the functions shownas are disclosed and described, v) those alternative designs and methodswhich accomplish each of the functions shown as are implicit toaccomplish that which is disclosed and described, vi) each feature,component, and step shown as separate and independent inventions, vii)the applications enhanced by the various systems or componentsdisclosed, viii) the resulting products produced by such systems orcomponents, ix) each system, method, and element shown or described asnow applied to any specific field or devices mentioned, x) methods andapparatuses substantially as described hereinbefore and with referenceto any of the accompanying examples, xi) an apparatus for performing themethods described herein comprising means for performing the steps, xii)the various combinations and permutations of each of the elementsdisclosed, xiii) each potentially dependent claim or concept as adependency on each and every one of the independent claims or conceptspresented, and xiv) all inventions described herein.

In addition and as to computer aspects and each aspect amenable toprogramming or other electronic automation, the applicant(s) should beunderstood to have support to claim and make a statement of invention toat least: xv) processes performed with the aid of or on a computer asdescribed throughout the above discussion, xvi) a programmable apparatusas described throughout the above discussion, xvii) a computer readablememory encoded with data to direct a computer comprising means orelements which function as described throughout the above discussion,xviii) a computer configured as herein disclosed and described, xix)individual or combined subroutines and programs as herein disclosed anddescribed, xx) a carrier medium carrying computer readable code forcontrol of a computer to carry out separately each and every individualand combined method described herein or in any claim, xxi) a computerprogram to perform separately each and every individual and combinedmethod disclosed, xxii) a computer program containing all and eachcombination of means for performing each and every individual andcombined step disclosed, xxiii) a storage medium storing each computerprogram disclosed, xxiv) a signal carrying a computer program disclosed,xxv) the related methods disclosed and described, xxvi) similar,equivalent, and even implicit variations of each of these systems andmethods, xxvii) those alternative designs which accomplish each of thefunctions shown as are disclosed and described, xxviii) thosealternative designs and methods which accomplish each of the functionsshown as are implicit to accomplish that which is disclosed anddescribed, xxix) each feature, component, and step shown as separate andindependent inventions, and xxx) the various combinations andpermutations of each of the above.

With regard to claims whether now or later presented for examination, itshould be understood that for practical reasons and so as to avoid greatexpansion of the examination burden, the applicant may at any timepresent only initial claims or perhaps only initial claims with onlyinitial dependencies. The office and any third persons interested inpotential scope of this or subsequent applications should understandthat broader claims may be presented at a later date in this case, in acase claiming the benefit of this case, or in any continuation in spiteof any preliminary amendments, other amendments, claim language, orarguments presented, thus throughout the pendency of any case there isno intention to disclaim or surrender any potential subject matter. Itshould be understood that if or when broader claims are presented, suchmay require that any relevant prior art that may have been considered atany prior time may need to be re-visited since it is possible that tothe extent any amendments, claim language, or arguments presented inthis or any subsequent application are considered as made to avoid suchprior art, such reasons may be eliminated by later presented claims orthe like. Both the examiner and any person otherwise interested inexisting or later potential coverage, or considering if there has at anytime been any possibility of an indication of disclaimer or surrender ofpotential coverage, should be aware that no such surrender or disclaimeris ever intended or ever exists in this or any subsequent application.Limitations such as arose in Hakim v. Cannon Avent Group, PLC, 479 F.3d1313 (Fed. Cir 2007), or the like are expressly not intended in this orany subsequent related matter. In addition, support should be understoodto exist to the degree required under new matter laws—including but notlimited to European Patent Convention Article 123(2) and United StatesPatent Law 35 USC 132 or other such laws—to permit the addition of anyof the various dependencies or other elements presented under oneindependent claim or concept as dependencies or elements under any otherindependent claim or concept. In drafting any claims at any time whetherin this application or in any subsequent application, it should also beunderstood that the applicant has intended to capture as full and broada scope of coverage as legally available. To the extent thatinsubstantial substitutes are made, to the extent that the applicant didnot in fact draft any claim so as to literally encompass any particularembodiment, and to the extent otherwise applicable, the applicant shouldnot be understood to have in any way intended to or actuallyrelinquished such coverage as the applicant simply may not have beenable to anticipate all eventualities; one skilled in the art, should notbe reasonably expected to have drafted a claim that would have literallyencompassed such alternative embodiments.

Further, if or when used, the use of the transitional phrase“comprising” is used to maintain the “open-end” claims herein, accordingto traditional claim interpretation. Thus, unless the context requiresotherwise, it should be understood that the term “comprise” orvariations such as “comprises” or “comprising”, are intended to implythe inclusion of a stated element or step or group of elements or stepsbut not the exclusion of any other element or step or group of elementsor steps. Such terms should be interpreted in their most expansive formso as to afford the applicant the broadest coverage legally permissible.The use of the phrase, “or any other claim” is used to provide supportfor any claim to be dependent on any other claim, such as anotherdependent claim, another independent claim, a previously listed claim, asubsequently listed claim, and the like. As one clarifying example, if aclaim were dependent “on claim 20 or any other claim” or the like, itcould be re-drafted as dependent on claim 1, claim 15, or even claim 25(if such were to exist) if desired and still fall with the disclosure.It should be understood that this phrase also provides support for anycombination of elements in the claims and even incorporates any desiredproper antecedent basis for certain claim combinations such as withcombinations of method, apparatus, process, and the like claims.

Finally, any claims set forth at any time are hereby incorporated byreference as part of this description of the invention, and theapplicant expressly reserves the right to use all of or a portion ofsuch incorporated content of such claims as additional description tosupport any of or all of the claims or any element or component thereof,and the applicant further expressly reserves the right to move anyportion of or all of the incorporated content of such claims or anyelement or component thereof from the description into the claims orvice-versa as necessary to define the matter for which protection issought by this application or by any subsequent continuation, division,or continuation-in-part application thereof, or to obtain any benefitof, reduction in fees pursuant to, or to comply with the patent laws,rules, or regulations of any country or treaty, and such contentincorporated by reference shall survive during the entire pendency ofthis application including any subsequent continuation, division, orcontinuation-in-part application thereof or any reissue or extensionthereon.

What is claimed is:
 1. A method of successively eluting components of afirst hydrocarbon sample and then a second, different hydrocarbonsample, said method comprising the steps of: entraining said firsthydrocarbon sample into and as part of a first run amount of a firstsolvent mobile phase, said first solvent mobile phase having a firstsolvent strength; passing said first run amount of said first solventmobile phase over a particular bulk quantity of a non-porous, highsurface energy stationary phase; reversibly adsorbing resins materialsof said first hydrocarbon sample onto said particular bulk quantity ofsaid non-porous, high surface energy stationary phase; passing saidfirst run amount of said first solvent mobile phase over a particularbulk quantity of an active stationary phase; eluting a saturatescomponent of said first hydrocarbon sample; passing a first run amountof a second solvent mobile phase over said particular bulk quantity ofsaid active stationary phase, said second solvent mobile phase having asecond solvent strength that is greater than said first solventstrength; eluting an aromatic component of said first hydrocarbonsample; passing a first run amount of a third solvent mobile phase oversaid particular bulk quantity of said non-porous, high surface energystationary phase, said third solvent mobile phase having a third solventstrength that is greater than said second solvent strength; eluting aresins component of said first hydrocarbon sample; entraining saidsecond, different hydrocarbon sample into and as part of a second runamount of said first solvent mobile phase; passing said second runamount of said first solvent mobile phase over said particular bulkquantity of said non-porous, high surface energy stationary phase;reversibly adsorbing resins materials of said second, differenthydrocarbon sample onto said particular bulk quantity of saidnon-porous, high surface energy stationary phase; passing said secondrun amount of said first solvent mobile phase over said particular bulkquantity of said active stationary phase; eluting a saturates componentof said second, different hydrocarbon sample; passing a second runamount of said second solvent mobile phase over said particular bulkquantity of said active stationary phase; eluting an aromatic componentof said second, different hydrocarbon sample; passing a second runamount of said third solvent mobile phase over said particular bulkquantity of said non-porous, high surface energy stationary phase; andeluting a resins component of said second, different hydrocarbon sample.2. A method of successively eluting components of a first hydrocarbonsample and then a second, different hydrocarbon sample as described inclaim 1 wherein said method of successively eluting components of afirst hydrocarbon sample and then a second, different hydrocarbon sampleis a method of successively eluting components of a first crude oilsample and then a second, different crude oil sample.
 3. A method ofsuccessively eluting components of a first hydrocarbon sample and then asecond, different hydrocarbon sample as described in claim 1 whereinsaid method of successively eluting components of a first hydrocarbonsample and then a second, different hydrocarbon sample is a method ofsuccessively eluting components of a first heavy oil sample and then asecond, different heavy oil sample.
 4. A method of successively elutingcomponents of a first hydrocarbon sample and then a second, differenthydrocarbon sample as described in claim 1 wherein said method ofsuccessively eluting components of a first hydrocarbon sample and then asecond, different hydrocarbon sample is a method of successively elutingcomponents of a first opportunity crude oil sample and then a second,different opportunity crude oil sample.
 5. A method of successivelyeluting components of a first hydrocarbon sample and then a second,different hydrocarbon sample as described in claim 1 wherein said methodof successively eluting components of a first hydrocarbon sample andthen a second, different hydrocarbon sample is a method of successivelyeluting components of a first maltenes sample generated from a first oiland then a second, different maltenes sample generated from a secondoil.
 6. A method of successively eluting components of a firsthydrocarbon sample and then a second, different hydrocarbon sample asdescribed in claim 1 further comprising the steps of reversiblyadsorbing highly aromatic materials of said first and second, differenthydrocarbon samples.
 7. A method of successively eluting components of afirst hydrocarbon sample and then a second, different hydrocarbon sampleas described in claim 1 further comprising the steps of analyzing saidsaturates, aromatics and resins components of said first and second,different hydrocarbon samples to generate analysis results.
 8. A methodof successively eluting components of a first hydrocarbon sample andthen a second, different hydrocarbon sample as described in claim 1further comprising the step of solvent flushing said particular bulkquantity of said non-porous, high surface energy stationary phase andsaid particular bulk quantity of said active stationary phase afterperforming said step of eluting a resins component of said firsthydrocarbon sample but before performing said step of entraining saidsecond, different hydrocarbon sample of a hydrocarbon into and as partof a second run amount of said first solvent mobile phase.
 9. A methodof successively eluting components of a first hydrocarbon sample andthen a second, different hydrocarbon sample as described in claim 1wherein said step of entraining said first hydrocarbon sample into andas part of a first run amount of a first solvent mobile phase comprisesthe step of entraining said first hydrocarbon sample into and as part ofa first run amount of a mobile phase that comprises a solvent selectedfrom the group consisting of: pentane, hexane, heptane, iso-octane, andtrimethylpentane.
 10. A method of successively eluting components of afirst hydrocarbon sample and then a second, different hydrocarbon sampleas described in claim 1 wherein said step of passing said first runamount of said first solvent mobile phase over a particular bulkquantity of a non-porous, high surface energy stationary phase comprisesthe step of passing said first run amount of said first solvent mobilephase over a particular bulk quantity of a stationary phase thatcomprises a medium selected from the group consisting of: glass,ceramics and metal.
 11. A method of successively eluting components of afirst hydrocarbon sample and then a second, different hydrocarbon sampleas described in claim 1 wherein said step of passing said first runamount of said first solvent mobile phase over a particular bulkquantity of an active stationary phase comprises the step of passingsaid first run amount of said first solvent mobile phase over aparticular bulk quantity of a stationary phase that comprises a mediumselected from the group consisting of: activity enhanced silica andactivity enhanced alumina.
 12. A method of successively elutingcomponents of a first hydrocarbon sample and then a second, differenthydrocarbon sample as described in claim 1 wherein said step of passinga first run amount of a second solvent mobile phase over a particularbulk quantity of an active stationary phase comprises the step ofpassing a first run amount of a toluene over a particular bulk quantityof an active stationary phase.
 13. A method of successively elutingcomponents of a first hydrocarbon sample and then a second, differenthydrocarbon sample as described in claim 1 wherein said step of passinga first run amount of a third solvent mobile phase over said particularbulk quantity of said non-porous, high surface energy stationary phasecomprises the step of passing a first run amount of methylenechloride:methanol over said particular bulk quantity of said non-porous,high surface energy stationary phase.
 14. A method of successivelyeluting components of a first hydrocarbon sample and then a second,different hydrocarbon sample as described in claim 1 further comprisingthe step of passing said first run amount of said first solvent mobilephase over a particular bulk quantity of less active stationary phasethat is distinct from said particular bulk quantities of saidnon-porous, high surface energy stationary phase and said activestationary phase, wherein said less active stationary phase is lessactive than said non-porous, high surface energy stationary phase andsaid active stationary phase.
 15. A method of successively elutingcomponents of a first hydrocarbon sample and then a second, differenthydrocarbon sample as described in claim 1 further comprising the stepof passing said first run amount of said first solvent mobile phase overa particular bulk quantity of an inert stationary phase.
 16. A method ofsuccessively eluting components of a first hydrocarbon sample and then asecond, different hydrocarbon sample as described in claim 15 whereinsaid inert stationary phase comprises polytetrafluoroethylene.
 17. Amethod of successively eluting components of a first hydrocarbon sampleand then a second, different hydrocarbon sample as described in claim 15further comprising the step of precipitating asphaltenes of said firsthydrocarbon sample within said inert stationary phase.
 18. A method ofsuccessively eluting components of a first hydrocarbon sample and then asecond, different hydrocarbon sample as described in claim 15 furthercomprising the step of passing at least one asphaltene solvent over saidparticular bulk quantity of said inert stationary phase.
 19. A method ofsuccessively eluting components of a first hydrocarbon sample and then asecond, different hydrocarbon sample as described in claim 18 furthercomprising the step of eluting an asphaltene component of said firsthydrocarbon sample.
 20. A method of successively eluting components of afirst hydrocarbon sample and then a second, different hydrocarbon sampleas described in claim 18 further comprising the step of passing saidsecond run amount of said first solvent mobile phase over saidparticular bulk quantity of an inert stationary phase.
 21. A method ofsuccessively eluting components of a first hydrocarbon sample and then asecond, different hydrocarbon sample as described in claim 20 furthercomprising the step of precipitating asphaltenes of said second,different hydrocarbon sample within said inert stationary phase.
 22. Amethod of successively eluting components of a first hydrocarbon sampleand then a second, different hydrocarbon sample as described in claim 20further comprising the step of passing at least one asphaltene solventover said particular bulk quantity of said inert stationary phase.
 23. Amethod of successively eluting components of a first hydrocarbon sampleand then a second, different hydrocarbon sample as described in claim 22further comprising the step of eluting an asphaltene component of saidsecond, different hydrocarbon sample.
 24. A method of successivelyeluting components of a first hydrocarbon sample and then a second,different hydrocarbon sample as described in claim 15 further comprisingthe step of passing said second run amount of said first solvent mobilephase over said particular bulk quantity of said inert stationary phase.25. A method of successively eluting components of a first hydrocarbonsample and then a second, different hydrocarbon sample as described inclaim 7 further comprising the step of using said analysis results toimprove a process selected from the group consisting of coking onsetestimation, oil processing, oil fractionating, oil production, pipelinefouling mitigation, hydrotreating, distillation, vacuum distillation,atmospheric distillation, visbreaking, blending, asphalt formation,asphalt extraction, and asphaltene content of oil measurement.
 26. Amethod of successively eluting components of a first hydrocarbon sampleand then a second, different hydrocarbon sample as described in claim 7further comprising the step of using said analysis results to further aprocessing related goal selected from the group consisting of:increasing distillate yield and quality; displacing high-sulfur fueloil; boosting propylene output; mitigating fouling and corrosion; andreducing carbon footprint.
 27. A method of successively elutingcomponents of a first hydrocarbon sample and then a second, differenthydrocarbon sample as described in claim 1 further comprising the stepof adding at least one additional material into and as part of at leastone of said first run amount of said first solvent mobile phase and saidsecond run amount of said first solvent mobile phase, wherein saidadditional material is selected from the group consisting of additiveand rejuvenator.